Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture

Abstract

Catalysts and processes are described to make low molecular weight, essentially terminally-unsaturated, viscous poly(1-olefin) or copoly(1-olefin) having a high terminal vinylidine content from a feed stock containing one or more 1-olefin and other volatile hydrocarbon liquids using a Ziegler catalyst made from a Group IVb metallocene and an aluminoxane cocatalyst, particularly bis(cyclopentadienyl) and bis(indenyl) titanium(IV), zirconium(IV) or hafnium(IV) compounds and methylaluminoxane. A particularly useful feed stock is a refinery stream containing 1-olefins and isobutylene which is used to make polyisobutylene. The reactive, essentially terminally-unsaturated, viscous poly(1-olefin) or copoly(1-olefin) can be functionalized to make a number of products useful as sealants, petroleum additives, adhesives, and the like by reacting the terminal vinylidine linkage with an aromatic, an epoxidation agent, a silylation agent, maleic anhydride, carbon monoxide and hydrogen, hydrogen, a halogen, a hydrohalogen, and the like.

What is claimed is: 
     
       1. A process to form an essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 80%, which comprises polymerizing under solution phase conditions a 1-olefin(s)-containing feed wherein the 1-olefin(s) in said feed consist essentially of one or more C 3  to C 20  1-olefins using a catalyst comprising a cyclopentadienyl or indenyl Periodic Group IVb metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, said feed containing at least about 1 wt. % isobutylene. 
     
     
       2. A process to form an essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin), which process comprises polymerizing under solution phase conditions a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins using a catalyst comprising a cyclopentadienyl or indenyl titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, to form a poly(1-olefin) or copoly(1-olefin) having molecular weight in a range from about 300 to about 10,000 and terminal vinylidene content of more than 80%. 
     
     
       3. The process of claim 2 wherein the cocatalyst is selected from the group consisting of linear methylaluminoxane, cyclic methylaluminoxane, and mixtures thereof. 
     
     
       4. The process of claim 3 wherein the catalyst comprises a member selected from the group consisting of bis(cyclopentadienyl) titanium(IV), zirconium(IV) and hafnium(IV) compounds, and bis(indenyl) titanium (IV), zirconium (IV), and hafnium (IV) compounds. 
     
     
       5. The process of claim 2 wherein the catalyst comprises a member selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride and bis(indenyl)zirconium dichloride. 
     
     
       6. The process of claim 2 wherein the feedstock contains at least about 0.1 wt. % of isobutylene, the catalyst comprises bis(indenyl)zirconium dichloride and methylaluminoxane cocatalyst, and wherein a poly(1-olefin) or copoly(1-olefin) having a molecular weight in a range from about 300 to about 5000 and a terminal vinylidene content greater than 90% is formed. 
     
     
       7. The process of claim 2 wherein said feedstock additionally contains up to about 70% by weight of an alpha-omega diene. 
     
     
       8. An essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) polymer having a molecular weight in a range from about 300 to about 10,000 and a terminal vinylidene content of more than 80%, which poly(1-olefin) or copoly(1-olefin) is made by polymerizing, under solution phase conditions, a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins using a catalyst comprising a cyclopentadienyl or indenyl titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater. 
     
     
       9. The polymer of claim 8 wherein the catalyst comprises a member selected from the group consisting of bis(cyclopentadienyl)zirconium dichloride and bis(indenyl)zirconium dichloride and a cocatalyst selected from the group consisting of linear methylaluminoxane, cyclic methylaluminoxane, and mixtures thereof. 
     
     
       10. A process to sequentially form polyisobutylene and an essentially-1-olefin-containing poly(1 -olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 80% from a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins, the feedstock containing between about 0.1 and 55 wt. % isobutylene, which process comprises the steps: (a) polymerizing under solution phase conditions the 1-olefin(s) using a catalyst comprising a cyclopentadienyl or indenyl titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, to form a poly(1-olefin) or copoly(1-olefin); and   (b) polymerizing the isobutylene with an acid catalyst to form polyisobutylene.   
     
     
       11. A process to form an essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 80%, which comprises polymerizing under solution phase conditions a olefin(s)-containing feed, wherein the 1-olefin(s) in said feed consist essentially of one or more C 3  to C 20  1-olefins, using a catalyst comprising a bis(indenyl) Periodic Group IVb metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, said feed containing at least about 1 wt. % isobutylene. 
     
     
       12. The process of claim 11 wherein the bis(indenyl) Periodic Group IVb metallocene is a bis(indenyl) zirconium(IV) compound. 
     
     
       13. The process of claim 12 wherein the bis(indenyl) Periodic Group IVb metallocene is bis(indenyl)zirconium dichloride. 
     
     
       14. A process to form an essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin), which process comprises polymerizing under solution phase conditions a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins using a catalyst comprising a bis(indenyl) titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, to form a poly(1-olefin) or copoly(1-olefin) having a molecular weight in a range from about 300 to about 10,000 and terminal vinylidene content of more than 80%. 
     
     
       15. The process of claim 14 wherein the bis(indenyl) metallocene is a bis(indenyl) zirconium(IV) compound. 
     
     
       16. The process of claim 15 wherein the bis(indenyl) metallocene is bis(indenyl)zirconium dichloride. 
     
     
       17. An essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 80%, which poly(1-olefin) or copoly(1-olefin) is made by polymerizing under solution phase conditions a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins using a catalyst comprising a bis(indenyl) titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater. 
     
     
       18. The process of claim 17 wherein the bis(indenyl) metallocene is a bis(indenyl) zirconium(IV) compound. 
     
     
       19. The process of claim 18 wherein the bis(indenyl) metallocene is bis(indenyl)zirconium dichloride. 
     
     
       20. A process to sequentially form polyisobutylene and an essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) of molecular weight between about 300 and about 10,000 that exhibits a terminal vinylidene content of more than 80% from a 1-olefin(s)-containing feedstock, wherein the 1-olefin(s) in said feedstock consist essentially of C 3  -C 20  1-olefins, comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C 3  to C 20  1-olefins, the feedstock containing between about 0.1 and 55 wt. % isobutylene, which process comprises the steps: (a) polymerizing under solution phase conditions the 1-olefin(s) using a catalyst comprising a bis(indenyl) titanium(IV), zirconium (IV) or hafnium(IV) metallocene and an aluminoxane cocatalyst, wherein the molar ratio of aluminoxane to metallocene is about 150 or greater, to form a poly(1-olefin) or copoly(1-olefin), and   (b) polymerizing the isobutylene with an acid catalyst to form polyisobutylene.   
     
     
       21. The process of claim 20 wherein the bis(indenyl) metallocene is a bis(indenyl) zirconium(IV) compound. 
     
     
       22. The process of claim 21 wherein the bis(indenyl) metallocene is bis(indenyl)zirconium dichloride.